Method of conditioning hair

ABSTRACT

A method of conditioning hair by applying thereto a quaternary ammonium polymers having formula ##STR1## wherein R&#39; and R&#34; may be the same or different alkyl groups of from 1 to 18 carbon atoms, optionally substituted by from 1 to 2 hydroxyl groups or, when taken together, with N form a saturated or unsaturated ring of from 5 to 7 atoms, or when taken together with N and an oxygen atom form the N-morpholino group; wherein Z is --CH 2  CH═CHCH 2  -- when Z&#39; is --CH 2  CHOHCH 2  -- or Z is --CH 2  CHOHCH 2  -- when Z&#39; is --CH 2  CH═CHCH 2  --; wherein X is a halogen of atomic weight greater than 30; wherein Y and Y&#39; may be either the same or different and may be either X or --NR&#39;R&#34;; and wherein n is an integer of from 2 to 20.

This is a division of Application Ser. No. 206,997, filed Nov. 17, 1980,now issued as U.S. Pat. No. 4,374,244, dated Feb. 15, 1983, the latterbeing a continuation-in-part of Application Ser. No. 29,778, filed Apr.13, 1979 now issued as U.S. Pat. No. 4,304,910, dated Dec. 8, 1981 whichis, in turn, a continuation-in-part of Application Ser. No. 902,894,filed May 4, 1978 and issued as U.S. Pat. No. 4,190,644, dated Feb. 26,1980, and that, in turn, was a continuation-in-part of Application Ser.No. 744,617, filed Nov. 24, 1976 and issued as U.S. Pat. No. 4,089,977on May 16, 1978. The disclosures of these prior applications areincorporated herein by reference.

PRIOR ART

A. U.S. Pat. Nos. 3,874,870, 3,923,973, 3,929,990, 3,931,319, 3,933,812,3,961,042, 4,001,432, 4,005,193, 4,012,446, 4,025,617, 4,025,653,4,026,945, 4,027,020, 4,035,480, 4,036,959, 4,055,712, and 4,091,113,all of which, as a group, disclose the preparation and properties oflinear polymeric quaternary ammonium compounds with repeating unit##STR2##

B. The aforementioned Application Ser. No. 29,778, U.S. Pat. Nos.4,089,977 and 4,190,644, as well as U.S. Pat. Nos. 4,140,798 and4,188,293, all, as a group, disclose the preparation and properties oflinear polymeric quaternary ammonium compounds with repeating unit##STR3##

The aforesaid prior art polymeric were synthesized by causingapproximately equimolar quantities of monomers X--Z--X and R'R"N--ZNR'R" to react, forming polymeric products that may be representedby the formula ##STR4## where Z is either --CH₂ CH═CHCH₂ -- or --CH₂CHOHCH₂ --, Y is either X or --NR'R", X is a halogen of atomic weightgreater than 30, n is an integer of from 2 to 20, and R' and R" (I) maybe the same or different alkyl groups of from 1 to 18 carbon atomsoptionally substituted by from 1 to 2 hydroxyl groups; or (II) whentaken together with N represents a saturated or unsaturated ring of from5 to 7 atoms; or (III) when taken together with N and an oxygen atomrepresent the N-morpholino group.

The prior art listed above also disclosed two methods of "capping" thesepolymers by placing quaternary ammonium groups at the two chain termini,thereby preventing the polymeric chain from propogating by way ofengaging in a quaternizing reaction. The "capped" polymers may berepresented by the formula ##STR5## where (I) R"', R^(IV) and R^(V) maybe the same or different alkyl groups of from 1 to 18 carbon atomsoptionally substituted by from 1 to 2 hydroxyl groups, or (II) R"' is alower alkyl group of from 1 to 4 carbon atoms and R^(IV) and R^(V) takentogether with N represent a saturated or unsaturated heterocyclic ringof from 5 to 7 atoms; or (III) R"' is a lower alkyl group of from 1 to 4carbon atom sand R^(IV) and R^(V) taken together with N and an oxygenatom represent the N-morpholino group; and the other symbols R', R", Z,n and x have the same meaning given to them previously.

DESCRIPTION OF INVENTION

A new system of linear polymeric quaternary ammonium materials has beendiscovered which, as a group, has antimicrobial properties generally atleast as effective as those previously prepared and described above,and, in addition, has cosmetic properties, especially hair careproperties, that are superior to the prior art compounds.

These new polymers may be represented by the formula ##STR6## where Z is--CH₂ CH═CHCH₂ -- when Z' is --CH₂ CHOHCH₂ --, or Z is --CH₂ CHOHCH₂ --when Z' is --CH₂ CH═CHCH₂ --, Y and Y' may be the same or different, andeither X or --NR'R", all the other symbols retaining the same meaningsas given above.

Close inspection of the molecular formulas of the prior art and of thepresent invention will reveal that the prior art polymers have only onerepeating unit along the linear chain, either ##STR7## but the presentinvention contains both of these units alternately bonded to each otheralong the linear polymeric chain so that the real repeating unit of theinvention, as disclosed in the formula, is either ##STR8##

The origin of two possible repeating units in the molecular formula canbe found in the method of synthesis. The new polymers may be made eitherfrom

    XCH.sub.2 CH═CHCH.sub.2 X+R'R"NCH.sub.2 CHOHCH.sub.2 NR'R",

or from

    XCH.sub.2 CHOHCH.sub.2 X+R'R"NCH.sub.2 CH═CHCH.sub.2 NR'R"

where X, R', and R" have the same meanings given above.

Thus, to illustrate by specific examples: ##STR9## where Y is either--N(CH₂ CH₂ OH)₂ or ##STR10## and ##STR11## where Y' is either --Cl or##STR12##

In the manner common to the writing of polymerization equations, theequations above are not balanced lest the plethora of stochiometricdetails mask the similarities and differences of the methods theydescribe.

The capped quaternary ammonium polymers of the present invention may berepresented by two different molecular formulas. The proper molecularformula depends on which monomers are used to make the polymer.

When the monomers are XCH₂ CH═CHCH₂ X and R'R"NCH₂ CHOHCH₂ NR'R", thecapped product may be represented by the molecular formula ##STR13## Butwhen the monomers are XCH₂ CHOHCH₂ X and R'R"NCH₂ NR'R", the cappedpolymeric product may be represented by the molecular formula ##STR14##where R'" R^(IV) and R^(V) have the same meaning they had in the cappedpolymers compounds of the prior art, and R', R", n and X have the samemeanings as those given above.

The capped derivatives of the quaternary ammonium polymers of thisinvention may be made by the two methods not unlike the methodsdescribed in the prior art.

In the first method a compound of the type R'R"N--Z--NR'R" is made toreact with a molar excess of a compound of the type X--Z'--X, therebyleading to polymers of formula ##STR15## where Z is --CH₂ CH═CHCH₂ --when Z' is --CH₂ CHOHCH₂ --, and Z is --CH₂ CHOHCH₂ -- when Z' is --CH₂--CH═CHCH₂ --. After divesting the mother liquors of unreacted startingmonomers, the residue is quaternized by adding a calculated quantity ofNR'"R^(IV) R^(V) in a second reaction. All symbols retain their priormeanings as disclosed above. Thus, as a specific example, ##STR16##Reacting the above product with a calculated amount of ##STR17## If(CH₃)NCH₂ CHOHCH₂ (CH₃)₂ and ClCH₂ CH═CHCH₂ Cl were the startingmonomers, the formula for the capped polymer would be ##STR18##

The method of preparing capped polymers described above is not thepreferred method because it involves two separate steps, first makingthe polymer with halogen termini, then capping the termini with a 3°amine.

The second method of making the capped polymers of this invention is thepreferred method because it involves only a single operation. In thismethod, a monomer of formula X--Z--X is made to react with the monomerR'R"N--Z'NR'R" in the presence of a tertiary amine RN'"R^(IV) R^(V) inratios such that the sum of the tertiary amino equivalents in thedi-amino monomer, and mono-amine, is approximately equal to the sum ofthe halogen equivalents in the di-halo monomer, and the number of molesof di-amino monomer is at least twice the number of moles of monoamine.This single reaction leads directly to the capped polymers of thisinvention.

The principle of the one reaction procedure is as follows: When adi-halo monomer reacts with one amino group of the di-amino monomer, itcreates a molecule with a halogen terminus. This halogen terminus mayreact with either a di-amino monomer or a tertiary amine molecule. Whenit reacts with the di-amino monomer, a molecule with two tertiary aminotermini is created. When it reacts with the mono tertiary amine, aquaternary ammonium terminus is created. Since the quaternized terminusmay no longer react with a monomer to extend the chain, the quaternaryterminus has "capped" this end of the molecule.

Whatever is true during the early stages of chain propogation alsopertains during the later stages of chain propogation. Thus, for chainpropogation to occur, a 3° amino terminus must react with a di-halomonomer, thereby producing a halogen terminus. The halogen terminus mustreact with a bis-3° amino terminus, for chain propogation. But, if thehalogen terminus reacts with a mono-tertiary amine molecule, aquaternary ammonium terminus is produced and the molecule becomes"capped" at the end.

The average molecular weight of the polymer depends, to a large extent,on the molar ratio of di-tertiary amino monomer to mono-tertiary aminemolecule. But, a sufficient number of mono-tertiary amino molecules mustbe present if the main product is to be "capped".

It has been found that the preferred molar ratio of bis-3° amine monomerto mono-3° amine molecule is 10:1. The two extreme acceptable ratios are20:1 and 2:1. A ratio outside this range will produce products with atleast one of its properties inferior.

Since the "capping" reaction is random, the range of molecular weightsin the product may be expected to be wider than in the two-reactionprocedure where polymerization runs its course before the capping.

The preferred one-reaction procedure was used almost exclusively in thepreparation of polymers of this invention. Only one two-step synthesiswas performed, mainly for the purpose of showing that this synthesis wasfeasible. The "same" polymeric products made by the one-step andtwo-step methods were chemically indistinguishable from each other bysimple methods, and had identical anti-microbial and cosmeticproperties.

The formula for the divalent 2-butene-1,4-diyl chain (--CH₂ CH═CHCH₂ --)represents both the cis and trans possibilities of this group, and also,what is most likely from a practical point of view, mixtures of thesetwo steric possibilities.

The specific products prepared and tested were synthesized from a 5%cis:95% trans mixture of 1,4-dichloro-2-butene, and also repeated with a30% cis:70% trans mixture of the monomer.

The 1,4-di-3° amino-2-butene monomers were made from each of the1,4-dichloro-2-butene isomer mixtures disclosed above by causing them toreact with 2° amines. No effort was made to determine whether thecis:trans ratio of the dichlorobutene was changed during the amination.

Since there were no observable differences in the anti-microbialeffectiveness or the hair-care properties in the two sets of productsmade from monomers originating from starting materials with differentcis:trans ratios, it was presumed that the steric differences of theproducts, due to different cis:trans ratios of the 2-butene group, doesnot alter the practical usefulness of the polymers.

In principle, a significant variance in this ratio might affect theaverage molecular weight of the product, and perhaps other properties,but this matter was not investigated.

Some of the reactions were repeated several times, each in a differentsolvent. The solvents were water, methanol, 95% ethanol, isopropanol anda 50:50 mixture by weight of water and isopropanol.

All the polymers were soluble in water, methanol and 95% ethanol, theproduct being a viscous solution containing about 30%-50% active solids.Sometimes the 95% ethanol solution deposited a little solid upon longstanding, but the solid dissolved when a little water was added.Isopropanol solvent did not dissolve the product. The insoluble polymerwas filtered out and dissolved in water. The anti-microbial andhair-care properties of this aqueous solution were identical to those ofthe similar product made in water. However, when a 50:50 mixture byweight of isopropanol and water was used as the reaction solvent, aclear viscous solution was the product.

The products of this invention, therefore, appear to be soluble inwater, methanol, 95% ethanol, and 50:50 isopropanol-water by weight, andinsoluble in pure isopropanol.

The following examples illustrate more clearly the procedural details ofmaking the compounds of this invention.

EXAMPLE 1

142 grams (1 mole) of 1,4-bis-(dimethylamino)-2-butene (R'=R"=--CH₃)made from 1,4-dichloro-2-butene, 5% cis, 95% trans; and 129 grams (1mole) of 1,3-dichloro-2-propanol and 500 grams of water were mixedthoroughly while heated to 80°-90° C. on a steam bath, and kept at thattemperature with constant stirring for 6 hours. Analysis of thehomogeneous viscous reaction product for ionic chloride indicated thatthe reaction was about 98% complete. The viscous liquid was subjected tosteam distillation to remove volatile material, namely unreactedmonomer. The residue contained about 35% active solids, and was used `asis` for testing.

The reaction was repeated, except that methanol, 95% ethanol,isopropanol and 50:50 mixture by weight of isopropanol and water wereused as solvents in separate reactions, instead of water. All productswere homogeneous viscous solutions except for the product made inisopropanol. In isopropanol the reaction mixture began to deposit solidpolymer shortly after the reaction commenced. The solid product wasfiltered off, dissolved in water, and the aqueous solution used fortesting.

EXAMPLE 2

The procedures disclosed in Example 1 were repeated, except that the1,4-bis-(dimethylamino)-2-butene was prepared from 1,4-dichloro-2-butenewhich was about 30% cis, and about 70% trans. There were no apparentdifferences between these products and the products synthesized inExample 1.

EXAMPLE 3

The procedures of Example 1 were followed, except that 1 mole of1,4-bis-(di-(2-hydroxyethlamino)-2-butene (R'=R"=--CH₂ CH₂ OH) was usedinstead of the 1,4-bis-(dimethylamino)-2-butene.

EXAMPLE 4

The procedure of Example 2 was followed, except that 1 mole of1,4-bis-(di-(2-hydroxyethylamino)-2-butene (R'=R"=--CH₂ CH₂ OH) was usedinstead of the 1,4-bis-(dimethylamino)-2-butene.

EXAMPLE 5

The procedure of Example 1 was used, using water only as a solvent, forthe bis amines in which:

    (a) R'=--C.sub.12 H.sub.25 and R"=--CH.sub.3 ##STR19##

EXAMPLE 6

125 grams (1 mole) of 1,4-dichloro-2-butene (5% cis, 95% trans) and 146grams (1 mole) of 1,3-bis-(dimethylamino)-2-propanol and 500 grams ofwater were mixed thoroughly while heated on a steam bath to 80°-90° C.,and kept at that temperature with constant stirring for 6 hours.Analysis of the reaction product for ionic chloride indicated that thereaction was about 98% complete. The viscous liquid was subjected tosteam distillation to remove volatile materials, namely unreactedmonomers. The residue contained about 35% active solids, and was used`as is` for testing.

The reaction was repeated except that methanol, ethanol and a 50:50mixture by weight of isopropanol and water were used as solvents, inseparate reactions, instead of water. All products were homogeneousviscous liquids containing about 35% active solids.

When the reaction was repeated using pure isopropanol as solvent, thereaction product was a solid. The solid was filtered off, dried,dissolved in water to known concentrations, and the aqueous solutionused for testing.

EXAMPLE 7

The procedures disclosed in Example 6 were repeated, except that the1,4-dichloro-2-butene was a mixture of about 30% cis and about 70%trans.

EXAMPLE 8

The procedures of Example 6 were followed except that 1 mole of1,3-bis-[(di-(2-hydroxyethylamino)-2-propanol was used instead of1,3-bis-(dimethylamino]-2-propanol.

EXAMPLE 9

The procedures of Example 7 were followed except that 1 mole of1,3-bis-[(di-(2-hydroxyethylamino)]-2-propanol was used instead of1,3-bis-(dimethylamino)-2-propanol.

EXAMPLE 10

The procedure of Example 6 was followed using water only as a solvent,for the bis-amines in which

    (a) R'=--C.sub.12 H.sub.25 and R'=--CH.sub.3 ##STR20##

EXAMPLE 11

142 grams (1 mole) of 1,4-bis-(dimethylamino)-2-butene (made from1,4-dichloro-2-butene, 5% cis, 95% trans) and 142 grams (1.1 moles) of1,3-dichloro-2-propanol and 500 grams of water were mixed thoroughlywhile heated at 80°-90° C., and kept at that temperature, with constantstirring, for 6 hours. After cooling, the unreacted monomers wereextracted with ether. The difference between analyses for total chlorideand ionic chloride indicated that 0.11 mole of terminal chloride waspresent. An aqueous solution containing 0.11 mole of trimethyl amine wasadded and the mixture stirred for 1 hour at room temperature, and 2hours at 80°-90° C., and then cooled. The viscous liquid had the sameproperties as the product made in Example 12.

EXAMPLE 12

128 grams (0.9 mole) of 1,4-bis-(dimethylamino)-2-butene (made from 5%cis, 95% trans, 1,4-dichloro-2-butene), and 129 grams (1.0 mole) of1,3-dichloro-2-propanol, and 30 grams (0.2 mole) of triethanolamine, and600 grams of water were mixed while heated on a steam bath to 80°-90°C., and kept at that temperature for 6 hours with constant stirring.Analysis of the viscous liquid product for ionic chloride indicated thatthe reaction was about 98% complete. It contained about 33% activesolids.

Half of the product was subjected to steam distillation for the purposeof removing any unreacted monomers or other volatile matter, but theresidue appeared to be identical to the undistilled portion.

EXAMPLE 13

The procedure of Example 12 was repeated, except that the1,4-bis-(dimethylamino)-2-butene was made from 30% cis, 70% trans,1,4-dichloro-2-butene. The product appeared to have identical propertiesto the product of example 12.

EXAMPLE 14

The procedure of Example 13 was repeated, except that the monoamine usedwas trimethylamine.

EXAMPLE 15

The procedure of Example 13 was repeated except that the monoamine usedwas docecyl dimethylamine (R'"=C₁₂ H₂₅ ; R^(IV) =--CH₃ ; R^(V) =--CH₃)

EXAMPLE 16

The procedure of Example 13 was repeated, except the monoamine used wasN-methyl morpholine ##STR21##

EXAMPLE 17

131 grams (0.9 mole) of 1,3-bis-(dimethylamino)-2-propanol and 125 gramsof 1,4-dichloro-2-butene (5% cis, 95% trans) and 29 grams oftriethanolamine (0.2 mole) and 600 grams of water were mixed whileheated on a steam bath to 80°-90° C., and kept at that temperature for 6hours with constant stirring. Analysis of the viscous liquid product forionic chloride indicated that the reaction was about 98% complete. Itcontained about 33% of active solids. Half of the product was subjectedto steam destillation for the purpose of removing any unreacted monomersor other violate matter, but the residue appeared to be identical to theundistilled portion.

The product of this reaction appeared to be indistinguishable from theproducts of examples 12 and 13.

EXAMPLE 18

The procedure of Example 17 was repeated, except that the1,4-dichloro-2-butene used was a mixture of 30% cis and 70% trans. Theproduct appeared to be indistinguishable from the product of Examples12, 13 and 17.

EXAMPLE 19

The procedure of Example 18 was repeated, except that the monoamine usedwas trimethylamine, instead of triethanolamine. The product appeared tobe indistinguishable from the product of Example 14.

EXAMPLE 20

The procedure of Example 18 was repeated except that the monoamine usedwas dodecyl dimethylamine.

EXAMPLE 21

The procedure of Example 18 was repeated, except that the monoamine usedwas N-methyl morpholine.

EXAMPLE 22

The procedure of Example 13 was repeated, except that the followingratios of diamine and monoamine were used in separate synthesis.

(a) 1,4-bis-(dimethylamino)-2-butene, 0.94 moles; triethanolamine, 0.12moles

(b) 1,4-bis-(dimethylamino)-2-butene, 0.85 moles; triethanolamine, 0.30moles

EXAMPLE 23

The procedure of Example 18 was repeated, except that the followingratios of diamine and monoamine were used in separate synthesis.

(a) 1,3-bis-(dimethylamino-2-propanol, 0.95 moles; triethanolamine, 0.1mole

(b) 1,3-bis-(dimethylamino)-2-propanol; 0.86 moles triethanolamine; 0.28moles

The polymers of the present invention are sufficiently soluble in waterto be incorporated as components of many cosmetic systems, particularlyhair care preparations. They can be formulated to be compatable withhigh concentrations of many surfactants ordinarily used in shampoos,rinses, and creams.

The present polymers, furthermore, are substantive to hair and theyimpart a smooth, soft feeling thereto. They also promote detangling andeasy combing of hair by diminishing "drag".

But, equally as important as these desirable hair-care properties, thereappears to be no noticable "buildup" of polymer on the hair aftercontinued use, so there is no subsequent "flaking off". These surprisingproperties are even more noticable with the present polymers than withany other similar polymers.

The hair-care properties were determined by studying the effects ofhair-care preparations containing these polymers on DeMeo hair tressesin a manner well known in the art.

With respect of hair-care properties, the "capped" polymers of thepresent invention were found to be superior to the "non-capped"polymers, although the latter compounds were equal to the performance ofsimilar previously known polymers.

The four polymers which gave the best results on the DeMeo tresses were:##STR22## That is, polymers in which (I) R'=R"=--CH₃ and R"'=R^(IV)=R^(V) =--CH₂ CH₂ OH; and (II) R'=R"=--CH₃ and R"'=R^(IV) =R^(V).

The bacterialogical properties of the compound of this invention weredetermined by performing simultaneous test with the most potentanti-microbial compound of the prior art namely, ##STR23## which wasused as the control. The following procedure was used:

1. 50 ml. of germicide solutions of pre-selected concentrations wereaspetically transferred to sterile 125 ml. flasks, then inoculated with0.5 ml. of 1/10 nutrient broth culture of (a) pseudonomas aeruginosaand/or (b) aerobactor aerogenes.

2. Simultaneously, as controls, identical concentrations of the mostactive anti-microbial compound of the prior art were transferred tosterile flasks and similarly inoculated.

3. At 30 or 60 minute intervals following inoculation, aliquot portionsof each germicide-organism mixture were plated in Tryptone GlucoseExtract agar and inoculated at 37° C. for 48 hours.

4. The plates were read to determine the numbers of surviving ORGANISMS.

5. The results at each concentration of compound were compared with thecontrol at the same concentration.

The compounds tested most thoroughly for bacterialogical activity werethe "capped" polymers in which

(I) R'=R"=CH₃ and R'"=R^(IV) =R^(V) =--CH₂ CH₂ OH and

(II) R'=R"=R'"=R^(IV) =R^(V) =--CH₃

In each instance, regardless of the cis:trans ratio, the monomers usedto prepare the polymer, the ratio of bis-amine to mono-amine, and theparticular organism used, each of these new compounds hadbacteriological activity which was at least equal to that of thecontrol. The uncapped polymer in which R^(I) =R^(II) =--CH₃, and thecapped polymers in which R^(I) =R^(II) =--CH₃ and R^(III) =R^(IV) =R^(V)=--CH₂ CH₂ OH or --CH₃, were tested for their flocculant properties inwater treatment by using the method described in U.S. Pat. No.4,190,644.

All three polymers produced flocs at a concentration of about 10 partsper million. Their effectiveness was the same with the two cis:transratios that were tested.

The invention claimed is:
 1. A method of conditioning the hair whichcomprises applying a hair conditioning effective amount to the hair of acompound or mixture of compounds having the structure: ##STR24## wherein(I)R' and R" may be the same of different alkyl groups of from 1 to 18carbon atoms, optionally substituted by from 1 to 2 hydroxyl groups or,(II) when taken together, will form a saturated or unsaturated ring offrom 5 to 7 atoms, or (III) when taken together with N and an oxygenatom form the N-morpholino group; wherein Z is --CH₂ CH═CHCH₂ -- when Z'is --CH₂ CHOHCH₂ -- or Z is --CH₂ CHOHCH₂ -- when Z' is --CH₂ CH═CHCH₂--; wherein X is a halogen of atomic weight greater than 30; wherein Yand Y' may be either the same or different and may be either X or--NR'R"; and wherein n is an integer of from 2 to
 20. 2. A method ofconditioning the hair which comprises applying a hair conditioningeffective amount to the hair of a compound or mixture of compoundscharacterized by the formula: ##STR25## wherein (I), R' and R" are thesame or different alkyl groups of from 1 to 18 carbon atoms optionallysubstituted by from 1 to 2 hydroxyl groups or (II) R' and R" togetherwith N from a 5 to 7 membered N-heterocyclic ring, or (III) R' and R"together with N and an oxygen atom form a N-morpholino group; andwherein (I) R'" R^(IV) and R^(V) may be the same or different alkylgroups of from 1 to 18 carbon atoms optionally substituted by from 1 to2 hydroxyl groups, or (II) R'" is a lower alkyl group of from 1 to 4carbon atoms and R^(IV) and R^(V) taken together with N represent a 5 to7 membered heterocyclic ring; or (III) R'" is a lower alkyl group offrom 1 to 4 carbon atoms and R^(IV) and R^(V) taken together with N andan oxygen atom represent the N-morpholino group; n is an integer of from2 to 20; and X is a halogen atom of an atomic weight greater than
 30. 3.A method of conditioning the hair which comprises applying a hairconditioning effective amount to the hair of a compound or mixture ofcompounds characterized by the formula: ##STR26## wherein (I), R' and R"are the same or different alkyl groups of from 1 to 18 carbon atomsoptionally substituted by from 1 to 2 hydroxyl groups or (II) R' and R"together with N form a 5 to 7 membered N-heterocyclic ring, or (III) R'and R" together with N and an oxygen atom form a N-morpholino group; andwherein (I) R'", R^(IV) and R^(V) may be the same or different alkylgroups of from 1 to 18 carbon atoms optionally substituted by from 1 to2 hydroxyl groups, or (II) R'" is a lower alkyl group of from 1 to 4carbon atoms and R^(IV) and R^(V) taken together with N represent a 5 to7 membered heterocyclic ring; or (III) R'" is a lower alkyl group offrom 1 to 4 carbon atoms and R^(IV) and R^(V) taken together with N andan oxygen atom represent the N-morpholino group; n is an integer of from2 to 20 and X is a halogen atom of an atomic weight greater than
 30. 4.The method of claim 1 wherein the compound or mixture of compoundscomprises a viscous solution containing 30 to 50% active solids and thesolvent is selected from the group consisting of water, alcohol andmixtures thereof.
 5. The method of claim 1 wherein the compound ormixture of compounds comprises a solid.
 6. The method of claim 2 whereinthe compound or mixture of compounds comprises a viscous solutioncontaining 30 to 50% active solids and the solvent is selected from thegroup consisting of water, alcohol and mixtures thereof.
 7. The methodof claim 2 wherein the compound or mixture of compounds comprises asolid.
 8. The method of claim 3 wherein the compound or mixture ofcompounds comprises a viscous solution containing 30 to 50% activesolids and the solvent is selected from the group consisting of water,alcohol and mixtures thereof.
 9. The method of claim 3 wherein thecompound or mixture of compounds comprises a solid.